Polymer compositions

ABSTRACT

Polymer compositions which are useful to improve water repellency and durability in fiber, nonwoven, textile, and paper compositions are disclosed. A method of improving water repellency and durability in fiber, nonwoven, textile, and paper compositions is also disclosed.

[0001] This invention relates to polymer compositions, more specificallythis invention relates to polymer compositions which are useful asbinders in fiber, nonwoven, textile, and paper compositions.

[0002] Fiber, nonwoven, textile, and paper compositions typically arecoated with polymeric binders to provide water repellency anddurability. Self cross-linking acrylic polymers and styrene/acrylicpolymers are typically used in these applications. There is a need forpolymeric binders which provide improved water repellency and durabilityin fiber, nonwoven, textile, and paper compositions.

[0003] U.S. Pat. No. 5,521,266 discloses a method for forming polymersfrom hydrophobic monomers. The disclosed method utilizes macromolecularorganic compounds which have a hydrophobic cavity to complex monomerswhich have low water solubility. This enables the formation of polymersfrom low water solubility monomers by emulsion polymerization. Suitablemonomers for use in the method for forming polymers include laurylmethacrylate.

[0004] U.S. Pat. No. 3,915,921 discloses interpolymers made by solutionpolymerization. The interpolymers contain hydrophobic monomers includingstearyl methacrylate, and certain carboxylic monomers including acrylicacid. The interpolymers are taught to be effective thickeners.

[0005] Despite the disclosure of the prior art, there is a continuingneed for polymeric binders which provide improved water repellency anddurability in fiber, nonwoven, textile, and paper compositions.

[0006] We have surprisingly found that the use of the polymercompositions of this invention provide improved water repellency anddurability in fiber, nonwoven, textile, and paper compositions.

[0007] The present invention provides a composition comprising anemulsion polymer comprising as polymerized units:

[0008] i) a) from 9.5 to 99.9 parts by weight of at least one C₁₂ to C₄₀alkyl ester of (meth)acrylic acid;

[0009] b) from 0 to 90 parts by weight of at least one less than C₁₅ethylenically unsaturated nonionic monomer;

[0010] c) from 0 to 90 parts by weight of at least one ethylenicallyunsaturated acid containing monomer or salts thereof; and

[0011] d) from 0.1 to 10 parts by weight of at least one cross-linkingmonomer; and

[0012] ii) from 0 to 10 parts by weight, based on the polymer weight ofat least one cross-linking agent,

[0013] provided that the composition contains 0.1 to 10 parts by weight,based on the polymer weight cross-linking monomer and cross linkingagent.

[0014] In another embodiment, the present invention provides a method ofimproving water repellency and durability in fiber, nonwoven, textile,and paper compositions comprising:

[0015] a) providing a composition comprising an emulsion polymercomprising as polymerized units:

[0016] i) from 9.5 to 100 parts by weight of at least one C₁₂ to C₄₀alkyl ester of (meth)acrylic acid;

[0017] from 0 to 90 parts by weight of at least one less than C₁₅ethylenically unsaturated nonionic monomer;

[0018] from 0 to 90 parts by weight of at least one ethylenicallyunsaturated acid containing monomer or salts thereof; and

[0019] from 0 to 10 parts by weight of at least one cross-linkingmonomer; and

[0020] ii) from 0 to 10 parts by weight, based on the polymer weight ofat least one cross-linking agent;

[0021] b) providing a substrate selected from the group consisting offiber, nonwoven, textile, and paper;

[0022] c) coating the substrate with the polymer composition; and

[0023] d) drying the coated substrate.

[0024] The present invention also provides an article comprising:

[0025] a substrate selected from the group consisting of fiber,nonwoven, textile, and paper coated with an emulsion polymer compositioncomprising as polymerized units:

[0026] i) from 9.5 to 100 parts by weight of at least one C₁₂ to C₄₀alkyl ester of (meth)acrylic acid;

[0027] from 0 to 90 parts by weight of at least one less than C₁₅ethylenically unsaturated nonionic monomer;

[0028] from 0 to 90 parts by weight of at least one ethylenicallyunsaturated acid containing monomer or salts thereof; and

[0029] from 0 to 10 parts by weight of at least one cross-linkingmonomer; and

[0030] ii) from 0 to 10 parts by weight, based on the polymer weight ofat least one cross-linking agent.

[0031] The compositions of this invention may be prepared by a singlestage or multi-stage process. The process may be an emulsionpolymerization such as the process described in U.S. Pat. No. 5,521,266.The process may also be solution polymerization followed byemulsification as described in U.S. Pat. No. 5,539,021, mini-emulsionpolymerization, or micro-emulsion polymerization. Emulsionpolymerization is preferred. In the process utilized for preparing thesamples within this application, a first stage was prepared by adding amonomer emulsion and sodium persulfate to a solution containingmethyl-β-cyclodextrin (“CD”), deionized water, and surfactant. The firststage was reacted at 85° C. A second stage was prepared by making asecond monomer emulsion and feeding the second monomer emulsion and asodium persulfate solution to the reacted first stage. The second stagewas reacted at 85° C.

[0032] The compositions of this invention contain as polymerized unitsfrom 9.5 to 100 parts by weight, preferably from 15 to 80 parts byweight, more preferably 20 to 70 parts by weight of at least one C₁₂ toC₄₀ alkyl ester of (meth)acrylic acid. It is preferred that the alkylester of (meth)acrylic acid be a C₁₂ to C₃₀ alkyl ester of (meth)acrylicacid. It is more preferred that the alkyl ester of (meth)acrylic acid bea C₁₂ to C₁₈ alkyl ester of (meth)acrylic acid. Suitable alkyl esters of(meth)acrylic acid include cetyl (meth)acrylate, stearyl (meth)acrylate,behenyl (meth)acrylate, and eicosyl (meth)acrylate. Beneficialproperties may be obtained by utilizing more than one C₁₂ to C₄₀ alkylester of (meth)acrylic acid.

[0033] The compositions of this invention also contain as polymerizedunits from 0 to 90 parts by weight, preferably 15 to 90 parts by weight,more preferably 20 to 80 parts by weight of at least one less than C₁₅ethylenically unsaturated nonionic monomer. Suitable less than C₁₅ethylenically unsaturated nonionic monomers for use in the preparationof the polymer compositions of this invention include, but are notlimited to (meth)acrylic ester monomers including methyl acrylate, ethylacrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methylmethacrylate, butyl methacrylate, hydroxyethyl methacrylate, andhydroxypropyl acrylate; acrylamide or substituted acrylamides; styreneor substituted styrene; vinyl acetate or other vinyl esters; vinylmonomers such as vinyl chloride, vinylidene chloride, N-vinylpyrolidone; and acrylonitrile or methacrylonitrile. Butyl acrylate,methyl methacrylate, and styrene are preferred. More preferred are butylacrylate and methyl methacrylate.

[0034] The compositions of this invention also contain as polymerizedunits from 0 to 90 parts by weight, preferably 0.1 to 50 parts byweight, more preferably 1 to 10 parts by weight ethylenicallyunsaturated acid containing monomer or salts thereof. Suitableethylenically unsaturated acid containing monomers include, but are notlimited to acrylic acid, methacrylic acid, crotonic acid, phosphoethylmethacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinylsulfonate, itaconic acid, fumaric acid, maleic acid, monomethylitaconate, monomethyl fumarate, monobutyl fumarate, and maleicanhydride. Acrylic acid and methacrylic acid are preferred. Methacrylicacid is more preferred.

[0035] The compositions of this invention also contain as polymerizedunits from 0.1 to 10 parts by weight, preferably 0.1 to 5 parts byweight, more preferably 0.1 to 3 parts by weight, based on the polymerweight of a cross-linker selected from a cross-linking agent and across-linking monomer. By cross-linker is meant a compound which has atleast 2 reactive groups which will react with acid groups found on themonomers of the compositions of this invention. Cross-linking agentsuseful in this invention include a polyaziridine, polyisocyanate,polycarbodiimide, polyamine, and a polyvalent metal. The cross-linkingagent is optional, and may be added after polymerization has beencompleted.

[0036] Cross-linking monomers are cross-linkers which are incorporatedwith the monomers of the compositions of this invention duringpolymerization. Cross-linking monomers useful in this invention includedivinyl benzene, (meth)acryloyl polyesters of polyhydroxylatedcompounds, divinyl esters of polycarboxylic acids, diallyl esters ofpolycarboxylic acids, diallyl dimethyl ammonium chloride, triallylterephthalate, methylene bis acrylamide, diallyl maleate, diallylfumarate, hexamethylene bis maleamide, triallyl phosphate, trivinyltrimellitate, divinyl adipate, glyceryl trimethacrylate, diallylsuccinate, divinyl ether, the divinyl ethers of ethylene glycol ordiethylene glycol diacrylate, polyethylene glycol diacrylates ormethacrylates, 1,6-hexanediol diacrylate, pentaerythritol triacrylate ortetraacrylate, neopentyl glycol diacrylate, cyclopentadiene diacrylate,the butylene glycol diacrylates or dimethacrylates, trimethylolpropanedi- or tri-acrylates, (meth)acrylamide, n-methylol (meth)acrylamide,mixtures thereof, and the like. (Meth)acrylamide, n-methylol(meth)acrylamide, and mixtures thereof are preferred. The amount ofcross-linker utilized is chosen such that the cross-linker does notinterfere with film formation.

[0037] Chain transfer agents may be used to control the molecular weightof the polymer composition. Suitable chain transfer agents includemercaptans, such as, for example, dodecylmercaptan. The chain transferagent may be used at from 0.1% to 10% based on the total weight of thepolymeric composition.

[0038] The polymer compositions of this invention are useful in fiber,nonwoven, textile, and paper compositions.

[0039] The polymer compositions of this invention are typically used infiber, nonwoven, textile, and paper compositions. A substrate such asfiber, nonwoven, textile, or paper is coated or treated with the polymercomposition by dipping the substrate in the polymer composition or byspraying the polymer composition onto the substrate. The coatedsubstrate is then dried at a temperature from ambient to 200° C. Thesubstrate may then be cured at temperatures from ambient to 200° C. Itis preferred that enough polymer composition is utilized to give abinder add-on of from 2% to 200% on finished product weight. It is morepreferred that enough polymer composition is utilized to give a binderadd-on of from 10% to 50% on finished product weight.

[0040] The following abbreviations are used throughout this patentapplication:

[0041] LMA=lauryl methacrylate

[0042] SMA=stearyl methacrylate

[0043] St=styrene

[0044] MMA=methyl methacrylate

[0045] BA=butyl acrylate

[0046] MAA=methacrylic acid

[0047] nDDM=n-dodecyl mercaptan

[0048] Id.=sample identification number

[0049] CD=methyl-β-cyclodextrin

[0050] g=grams

[0051] ° C.=degrees centigrade

[0052] (meth)acrylate=methacrylate and acrylate

[0053] cc=cubic centimeter

[0054] MMAM=50% methacrylamide/50% n-methylol methacrylamide

[0055] cm=centimeter

[0056] MAM=90% n-methylol acrylamide/10% acrylamide

[0057] mm=millimeter

[0058] oz/sq yd=ounce/square yard

[0059] ml=milliliter

[0060] psi=pounds per square inch

[0061] Abs.=absorbance

[0062] RH=relative humidity

[0063] wt=weight

[0064] rpm=rotations per minute

[0065] The following Table lists some of the materials used in thispatent application and their sources: Material Function Source Triton ®XN-45S surfactant Union Carbide FC ® -280 fluorochemical 3M CompanyMichem Lube ® 743 wax McGee Mikon ® NRW-3 surfactant Sequa ChemicalCompany Aircel ® PC-6A methylated melamine Borden (Astro Industries)Cymel ® 303 melamine Cytek Scotch ® Magic Tape Tape 3M Company Triton ®X-100 surfactant Union Carbide

EXAMPLE 1

[0066] For stage 1, 400 g deionized water, 11.9 g Triton® XN-45S anionicsurfactant (58%), and CD (Table 1, 53% solution in water) wereintroduced into a 4-liter round bottom flask with four necks equippedwith a mechanical stirrer, temperature control device, condenser,monomer and initiator feed lines, and a nitrogen inlet at roomtemperature. The contents were heated to 85° C. while stirred under anitrogen purge. A monomer emulsion of 31.3 g deionized water, 0.4 gTriton® XN-45S anionic surfactant, 33.8 g LMA, 7.5 g BA, 33 g MMA, and0.75 g MAA was prepared separately. Solutions of 0.35% by weight sodiumcarbonate (based on the total monomer weight in stage 1 and stage 2) in25 g deionized water and 0.35% by weight sodium persulfate (based on thetotal monomer weight in stage 1 and stage 2) in 30 g deionized waterwere introduced into the reaction kettle. The monomer emulsion was fedover a period of 20 minutes together with an initiator solution of 0.05%sodium persulfate (based on the total monomer weight in stage 1 andstage 2) in 210 g deionized water.

[0067] For stage 2, a monomer emulsion was prepared using 625 gdeionized water, 7.8 g Triton® XN-45S anionic surfactant, and monomersaccording to Table 1. Immediately after the end of the stage 1 monomeremulsion feed, the stage 2 monomer emulsion was fed over a period of 3hours together with the sodium persulfate initiator solution. TABLE 1Id. LMA SMA BA MMA MAA MAM MMAM CD 1 300 0 525 660 15 0 0 14.3 2 675 0225 585 15 0 0 14.3 3 780 0 0 705 15 0 0 14.3 4 0 975 0 480 15 0 30 28.65 0 975 0 510 15 0 0 28.6 6 0 750 285 450 15 0 0 28.6 7 750 0 435 270 1530 0 14.3 8 0 975 0 480 15 30 0 28.6 9 750 0 735 0 15 0 0 14.3 10 0 9750 510 15 0 0 28.6

[0068] Samples 4, 7, and 8 are examples of the compositions of thisinvention. All samples demonstrate the usefulness of the compositions infiber, nonwoven, textile, and paper applications.

EXAMPLE 2 Application Testing—Impact Penetration Test

[0069] The impact penetration test measures the resistance of fabrics tothe penetration of water by impact. (AATCC Test Method 42-1989) Samplesthat perform well in this test as indicated by water penetration of lessthan 1 g are considered to be good candidates as coatings/treatments fornonwoven and paper compositions.

[0070] To prepare samples for the test, a pulp substrate (Whatman FilterPaper No:4) was padded with a composition of this invention. The bathsolids were 35% and the pad pressure was approximately ¾ bar. Sampleswere dried/cured for 3 minutes at 149° C. to give a binder add-on of 26%on finished product weight. The sample was tested in triplicate and theresults were averaged.

[0071] The Impact Penetration test was run by pouring 500 mils of waterthrough a spray nozzle and letting it impact a test fabric at a 45°angle and then measuring the amount of the water that penetrated the weband collected on a piece of blotter paper underneath the test sample.The results are shown in Table 2. TABLE 2 Sample Amount of waterpenetration (g) 6 0.3

[0072] The above data shows that a pulp substrate bonded with anSMA-containing composition is useful as a coating in nonwoven and papercompositions.

EXAMPLE 3 Application Testing—Water Absorption

[0073] The water absorption test was run to evaluate the hydrophobicproperties of the compositions of this invention by measuring thepercent water absorption of dried/cured films. Samples which performwell in this test as indicated by a percent water absorption of lessthan 35% are considered to be useful as coatings/treatments in nonwoven,textile, and paper compositions.

[0074] A film was prepared by drying latex in a container overnight. Thefilm was then fully dried/cured for 3 minutes at 149° C. Film thicknessranged from 10-15 mils. The percent water absorption of various polymerswas determined on dried/cured film samples with dimensions of 2.54cm×2.54 cm×10 mils after allowing the films to soak in water for 48hours. Samples were run in duplicate and averaged. The percent waterabsorption was determined for the compositions of this invention byusing the following equations:${\% \quad {Water}\quad {Absorption}} = {\frac{{Wf} - {Wi}}{Wi} \times 100}$

[0075] Where

[0076] Wi=the initial weight of the film

[0077] Wf=the final weight of the film after soaking in water for 48hours.

[0078] The results are shown in Table 3. TABLE 3 Sample Percent WaterAbsorption 6 14.6 3 12.4 5  7.9

[0079] The data above indicates that the compositions are useful ascoatings/treatments in nonwoven, textile, and paper compositions.

EXAMPLE 4 Application Testing—Tensile Testing and Handle-O-Meter

[0080] This test was run to demonstrate the utility of the compositionsof this invention as coatings/treatments for nonwovens. It is known thatpolymers with high strength as indicated by tensile strength, normallyare not acceptably soft. The acceptability of the binder is determinedby scores of greater than 1,000 g for dry tensile; greater than 600 gfor wet tensile; and greater than 300 g for isopropanol (IPA). Theacceptable score for Handle-O-Meter is 50 grams force or less.

[0081] Pad Saturation: A 1 oz/sq. yd. polyester web was saturated withbinder and dried/cured at 149° C. for 3 minutes. All samples hadapproximately 40% binder add-on based on fiber weight. From these samplewebs tensile and Handle-O-Meter testing was done. The saturationformulation was as follows (8% Bath solids):

[0082] 211.6 g Binder

[0083] 4.8 g Catalyst 1.5% solids on solids (25% NH₄NO₃)

[0084] 783.6 g Water

[0085] Tensile Testing: A 2.54×12.7 cm web sample with long axis in thecross machine direction was evaluated using a Intelect 500 Thwing AlbertTesting Instrument. The instrument was set to have a 10.2 cm gaugelength and a crosshead speed of 30.5 cm/minute. Dry, wet and Isopropanoltensile testing was done on an average of at least 7 sample strips. Wettensiles were obtained by soaking the web strips in 0.1% Triton® X-100surfactant for 30 minutes. Isopropanol tensiles were obtained by soakingthe web strips for 30 minutes in Isopropanol. Results were reported ingrams/2.54 cm.

[0086] Handle-O-Meter: Handle-O-Meter measurements were obtained from a10.2×10.2 cm web sample. Measurements were made using a Thwing AlbertDigital Handle-O-Meter (Model 211-5) using a 0.64 cm gap. The instrumentmeasured the resistance to bend the nonwoven through a slit of a certainwidth. Results were reported in grams force. An average reading ofmachine and crossmachine direction from at least four samples each wasobtained. The results of Tensile and Handle-O-Meter testing are shown inTable 4. TABLE 4 Dry Wet IPA Sample Tensile Tensile TensileHandle-O-Meter 5 2092 1339 546 107 90% 7/10% 8 (blend) 1155  870 358  42

[0087] The compositions have acceptable softness of hand and offerexcellent dry and wet tensile strength, and therefore are useful ascoatings/treatments in nonwoven compositions.

EXAMPLE 5 Application Testing—Mason Jar Test for Water Repellency

[0088] This test was run to evaluate the water repellent/barrierproperties of the compositions of this invention. The Mason Jar Testmeasured the resistance of a nonwoven fabric to the penetration of anaqueous sodium chloride solution under a hydrostatic head. This test canbe used to measure how well a medical nonwoven fabric repels fluids.Samples are considered to be acceptable when they demonstrate a score of120 minutes or greater.

[0089] The test was run by placing a swatch of the test fabric in placeof the flat metal lid, adding 510 mls of 0.9% saline solution to thejar, inverting the jar (which has a hole in the bottom to equalize thepressure) and measuring the time it takes for the water to penetrate thefabric.

[0090] The samples used for the Mason Jar test were prepared in thefollowing manner: A 1 oz/sq.yd. polyester web was padded using abinder/fluorochemical/wax bath. The solids of the bath were 35% and thepadder pressure was ¾ bar. A composition of this invention wasevaluated. The padded samples were dried/cured for 3 minutes at 149° C.Total binder add-on was approximately 40% (based on finished productweight). Each sample was tested by the Mason Jar Test in triplicate andthe results were averaged. The pad formulation was as follows (35% bathsolids):

[0091] 111 g Binder

[0092] 8.1 g FC®-280 (5.6% Solids on binder solids)

[0093] 18.75 g Michem Lube® 743 (wax) (12.0% Solids on Binder solids)

[0094] 1.25 g Mikon® NRW-3 (2.5% Wet on binder solids)

[0095] 30 g Water

[0096] The results are shown in Table 5. TABLE 5 Sample Time 6 120-300minutes

[0097] The sample demonstrated an acceptable score and, therefore isconsidered useful as a coating/treatment for medical nonwovencompositions.

EXAMPLE 6 Application Testing—Water Vapor Transmission

[0098] This test was run to determine the rate for water to permeatethrough a film. Samples that perform well in this test, as indicated bya WVTR of 1 g/hour× meter squared are considered to be useful innonwoven applications.

[0099] The test method used was Water Cup Method of ASTM E96-80. In thismethod, 30 mils of distilled water was added to a plastic cup. A polymerfilm (15-20 mils thick) which was dried/cured at 149° C. for 3 minuteswas then placed over and sealed to the mouth of the cup using a threadedplastic ring. The cup was then placed in a constant temperature andhumidity room (24° C./50% relative humidity) and periodic weighings ofthe cup were made to determine the rate of water movement through thepolymer film to the controlled atmosphere. The weight loss was plottedagainst time until a nominal steady state existed. The slope of thestraight line was the water vapor transmission rate. The water vaportransmission rate (WVTR) was determined using the following equation:${WVTR} = \frac{G}{\left( {T \times A} \right)}$

[0100] Where:

[0101] G=weight change

[0102] T=time

[0103] A=test area (mouth cup area)

[0104] WVTR was expressed in units of grams/hour×meter sq.

[0105] The results are shown in Table 6. TABLE 6 Sample WVTR 5 0.19g/hour x meter sq

[0106] The composition provides a good moisture barrier and therefore isconsidered to be useful as a coating/treatment in nonwoven compositions.

EXAMPLE 7 Application Testing—Flock Evaluation

[0107] This test was run to determine the potential for the compositionsof this invention to be used as binders for flocked fiber applications.

[0108] Flock formulations were a blend of 70% 9/30% 10 which were mixedwith 5% Clay and 1% Ammonium Stearate. The samples were formulated toapproximately 43% solids and a Brookfield LVT viscosity of 19,000 millipascal seconds (#4 spindle at 6 rpm). Osnaburg Polyester Cotton Fabricwas the substrate for testing. The target add-on was 2.5-3.0 oz/sq yd.The sample was flocked with 3 denier flock using alternating current.The Flocked fabrics were dried and cured for 3 minutes at 150° C.Samples were evaluated with and without 2% Aircel PC-6A (melamineformaldehyde cross-linker). The Flocked fabrics were evaluated for:

[0109] wash durability—cuff edge abrasion after five hot wash cycles,acceptable scores are between 4 and 5; and the British two pense scufftest evaluating abrasion, acceptable retention of scuff wet versus dryis greater than 30%. The scuff test was modified for flocked fabrics,counting the number of scuffs it took until adhesive failure was noted.The tests were run dry and wet. The results are shown in Tables 7, and8. TABLE 7 Flocked Fabric Evaluation (Wash Test) Sample Result Rating70% 9/30% 10 Complete flock removal 1 70% 9/30% 10 with Cymel 303 >90%flock retention 4

[0110] TABLE 8 Retained Wet Abrasion (British Two Pense Test) SampleResult 70% 9/30% 10 59% 70% 9/30% 10/Aircel ® PC-6A 91%

[0111] The above results indicate that the compositions are useful asbinders for fiber applications.

EXAMPLE 8 Applications Testing—Decorative Laminates

[0112] These tests were performed to demonstrate the utility of thecompositions of this invention as binders in decorative laminateapplications.

[0113] Saturant Composition: Latex/urea formaldehyde resin mixtures wereprepared at 38% total latex and urea formaldehyde resin solids. Fiftyparts of latex solids were combined with 50 parts of urea formaldehyderesin solids.

[0114] Saturation of sheets: A paper sheet was saturated using the abovemixture by first floating the pre-weighed sheet on the mixture surfacefor 20 seconds, followed by immersion for 10 seconds. The penetrationtime was recorded as the elapsed time (in seconds) required for thesaturant to completely strike through from the bottom side to the topsurface of the sheet. Immediately after completing the saturation, thesheet was passed through a padder using a single pass at 12 psi toremove excess saturant. The wet sheet was weighed and the % pick up wascalculated. The saturated sheet was cured for 2 minutes at 150° C.Acceptable scores for % pick-up are 20% to 60%.

[0115] Water Absorptiveness (Cobb Test): A modified procedure of TAPPITest Method T 441 om-84 was used to conduct this test. The methodmeasured the quantity of water absorbed by the paper in a specified timeunder standardized conditions. A 12.7 cm by 12.7 cm square sample wastested. The procedure was modified to use 25 ml water instead of the 100ml specified in the method, reducing the head from 1.0 cm to 0.25 cm.The test period was shortened from 120 seconds to 60 seconds. One ply ofpaper was tested at a time. The absorptiveness was calculated as theweight of water absorbed in grams per square meter. Acceptable scoresare less than 20 grams per square meter.

[0116] Flexibility: Flexibility of the paper was determined bypre-conditioning three 1.5 cm by 4 cm specimens at 50% relative humidityand 21° C. for 24 hours and rapidly bending the specimens over amandrel. A single test strip afforded testing of at least 3 differentmandrel sizes. The mandrel diameter, measured to mm, which did not causecracking of the sample surface was recorded as the pass point. Theaverage of the 3 passing values was reported as the flexibility at 50%relative humidity. Smaller mandrel diameter correlated with increasingflexibility. Flexibility at low relative humidity was measured by drying3-1.5 cm by 4 cm specimens for 5 minutes at 85° C. in a forced air oven,followed by rapidly bending the sample strip over the mandrel. Theaverage mandrel diameter which did not cause cracking of the paper underthese conditions was reported as the flexibility at low humidity.Acceptable scores for 50% RH and low % RH are less than 30 millimeters.

[0117] Scotch Tape Delamination Resistance: This test measured thecohesive strength of a single ply of paper to delamination of the plywhen a 2.54 cm by 2.54 cm surface of the paper was contacted with ScotchMagic Tape™ for 5 seconds and for 24 hours at conditions of 50% relativehumidity and 21° C. At each time interval, the tape was rapidly pulledby hand from the paper in the opposite direction from which the tape wasapplied. The percentage of the tape surface within the 2.54 cm contactarea which showed no evidence of fiber removal was recorded as thedelamination resistance of the sample immediately (5 seconds) afterapplication of the tape or after 24 hours of contact. Acceptable scoresare greater than 50%. The results of these tests are shown in Tables 9and 10. TABLE 9 Sample Penetration Speed Wt % Dry Pick-Up 1 1 46 2 146.2

[0118] TABLE 10 Tape Delamination Cobb Resistance Mandrel Flexibility(mm) Sample Water Abs. Initial 24 Hours 50% RH Low % RH 1 8.5 100 731.75 2.8 2 6.5  97 78 1.5  3.1

[0119] The data above indicate that the compositions are useful indecorative laminant applications.

What is claimed:
 1. A composition comprising an emulsion polymercomprising as polymerized units: i) a) from 9.5 to 99.9 parts by weightof at least one C₁₂ to C₄₀ alkyl ester of (meth)acrylic acid; b) from 0to 90 parts by weight of at least one less than C₁₅ ethylenicallyunsaturated monomer; c) from 0 to 90 parts by weight of at least oneethylenically unsaturated acid containing monomer or salts thereof, andd) from 0.1 to 10 parts by weight of at least one cross-linking monomer;and ii) from 0 to 10 parts by weight, based on the polymer weight of atleast one cross-linking agent, provided that the composition contains0.1 to 10 parts by weight, based on the polymer weight cross-linkingmonomer and cross linking agent.
 2. A composition according to claim 1wherein the composition comprises: a) from 40 to 99 parts by weight ofat least one C₁₂ to C₄₀ alkyl ester of (meth)acrylic acid, b) from 0 to50 parts by weight of at least one monomer selected from the groupconsisting of methyl methacrylate and butyl acrylate; c) from 0 to 50parts by weight methacrylic acid; and d) from 0.1 to 5 parts by weightof at least one cross-linking monomer selected from the group consistingof (meth)acrylamide, n-methylol (meth)acrylamide, and mixtures thereof.3. A composition according to claim 1 wherein the composition comprises:a) from 90 to 98 parts by weight of stearyl (meth)acrylate, b) from 1 to20 parts by weight of methyl methacrylate; c) from 1 to 15 parts byweight methacrylic acid; and d) from 0.1 to 3 parts by weight ofn-methylol methacrylamide.
 4. A method of improving water repellency anddurability in fiber, nonwoven, textile, and paper compositionscomprising: a) providing a polymer composition comprising as polymerizedunits: i) from 9.5 to 100 parts by weight of at least one C₁₂ to C₄₀alkyl ester of (meth)acrylic acid; from 0 to 90 parts by weight of atleast one less than C₁₅ ethylenically unsaturated monomer; from 0 to 90parts by weight of at least one ethylenically unsaturated acidcontaining monomer or salts thereof; and from 0 to 10 parts by weight ofat least one cross-linking monomer; and ii) from 0 to 10 parts byweight, based on the polymer weight of at least one cross-linking agent;b) providing a substrate selected from the group consisting of fiber,nonwoven, textile, and paper; c) coating the substrate with the polymercomposition; and d) drying the coated substrate.
 5. The method of claim4 wherein the polymer composition comprises: a) from 40 to 99 parts byweight of at least one C₁₂ to C₄₀ alkyl ester of (meth)acrylic acid, b)from 0 to 50 parts by weight of at least one monomer selected from thegroup consisting of methyl methacrylate and butyl acrylate; c) from 0 to50 parts by weight methacrylic acid; and d) from 0.1 to 5 parts byweight of at least one cross-linking monomer selected from the groupconsisting of (meth)acrylamide, n-methylol (meth)acrylamide, andmixtures thereof.
 6. An article comprising: a substrate selected fromthe group consisting of fiber, nonwoven, textile, and paper coated witha polymer composition comprising as polymerized units: i) from 9.5 to100 parts by weight of at least one C₁₂ to C₄₀ alkyl ester of(meth)acrylic acid; from 0 to 90 parts by weight of at least one lessthan C₁₅ ethylenically unsaturated monomer; from 0 to 90 parts by weightof at least one ethylenically unsaturated acid containing monomer orsalts thereof; and from 0 to 10 parts by weight of at least onecross-linking monomer; and ii) from 0 to 10 parts by weight, based onthe polymer weight of at least one cross-linking agent.
 7. An articleaccording to claim 6 wherein the polymer composition comprises: a) from40 to 99 parts by weight of at least one C₁₂ to C₄₀ alkyl ester of(meth)acrylic acid, b) from 0 to 50 parts by weight of at least onemonomer selected from the group consisting of methyl methacrylate andbutyl acrylate; c) from 0 to 50 parts by weight methacrylic acid; and d)from 0.1 to 5 parts by weight of at least one cross-linking monomerselected from the group consisting of methacrylamide, n-methylolmethacrylamide, and mixtures thereof.